This invention relates to colorants comprising a chromophore having two azo acetoacetanilide moieties, wherein said moieties each have at least one poly(oxyalkylene) chain, preferably at least two such chains. Such colorants exhibit excellent good base stability and lightfastness, particularly when incorporated within certain media and/or on the surface of certain substrates. These poly(oxyalkylene) chains provide solubility in different solvents or resins thereby permitting the introduction of such excellent coloring chromophores within diverse media and/or or diverse substrates. Compositions and articles comprising such colorants are provided as are methods for producing such inventive colorants.
All U.S. patents cited within this specification are hereby incorporated by reference.
Bis-acetoacetanilide azo pigments, dyes, and dyestuffs generally provide effective and desirable colorations to certain substrates, such as textiles, paper, and the like. However, their use is limited to such a narrow range of substrates and/or media due to the difficulty of solubility, comparability, and migratory problems inherent with such pigments, dyes, or dyestuffs. Such pigments, dyes, and/or dyestuffs have not been widely introduced as colorants within plastics (such as polyolefins, polyurethanes, and the like) due to such physical limitations. However, the utilization of such colorants is highly desired for a number of reasons, foremost the actual colorations available from such specific compounds.
The standard types of polymeric colorants now utilized within plastics (be they thermoplastics or thermoset types) are primarily poly(oxyalkylenated) compounds, such as triphenylmethanes, methines, and the like (i.e., those found within U.S. Pat. No. 4,992,204, to Kluger et al.). Some of these colorants exhibit certain problems in association with the catalysts utilized to effectuate plastic formation. For example, the triphenylmethane and methine moieties of such colorants are susceptible to attack by nucleophilic catalysts and their residues. As a result, the colorations provided by such polymeric colorants may be reduced in strength or changed in shade under such circumstances.
There is thus a desire to introduce such polymeric colorants having bis-acetoacetanilide groups therein within different types of compositions and therefore a desire to provide a bis-acetoacetanilide-type colorant containing polyoxyalkylene chains that can be tailored for versatility. Furthermore, there is a need to provide a colorant for introduction within thermoplastic and thermoset compositions which is far less susceptible to degradation due to attack by basic catalyst residues than the standard poly(oxyalkylenated) colorants of use today. To date, there have been no teachings or fair suggestions of such a highly desirable, specific polymeric bisacetoacetanilide colorant within the pertinent prior art or within the colorant industry itself.
It is thus an object of the invention to provide base stable yellow polymeric colorants for utilization within thermoplastic and thermoset articles. Another object of this invention to provide a yellow polymeric colorant exhibiting amide groups rather than base-susceptible methine moieties, which are thus less susceptible to attack by basic thermoplastic and thermoset catalysts, are easy to process, mixes well within target plastics, and provides excellent colorations within the target finished articles. Yet another object of this invention is to provide excellent colorations within liquid compositions (such as inks, and the like) through the utilization of water-soluble, liquid polymeric colorants, as noted above.
It is to be understood that the term alkyl as used throughout is intended to encompass any straight or branched alkyl moiety, having anywhere from 1 to 30 carbons therein; the same chain length applies to the term xe2x80x9calkoxyxe2x80x9d as well. Also, the terms substituted phenyl and substituted polyphenyl are intended to encompass any phenyl system having any type of pendant group attached thereto, including, without limitation, alkyl groups, alkylene groups, alcohol groups, ether groups, ester groups, amine groups, amide groups, hydroxyls, and the like. Phenyl is basically an unsubstituted ring system (and thus includes hydrogens only).
The present invention preferably encompasses poly(oxyalkylenated) acetoacetanilide azo colorants, particularly of the structure of Formula (I) 
wherein R is alkyl, phenyl, polyphenyl, substituted phenyl, or substituted polyphenyl; E is hydrogen alkyl, halogen, alkoxy, or phenyl; a is 0, 1, or 2, wherein if a is 0 then A is phenyl, polyphenyl, substituted polyphenyl, or substituted phenyl, if a is 1, then A is O, SO2N, methylene, S, N(Rxe2x80x2) or a moiety of Structure (II) 
wherein Rxe2x80x2 is alkyl or hydrogen, and if a is 2, then A is O, SO2, methylene, S, N(Rxe2x80x2), wherein Rxe2x80x2 is alkyl of hydrogen; B is Rxe2x80x3(gly)w[(EO)x(PO)y(EO)2EG]nxe2x80x3 wherein EG is H or a moiety of Structure (III) 
wherein R4 is C1-C12 alkyl or phenyl; all wherein gly is glycidol, EO is ethylene oxide, and PO is selected from the group consisting of propylene oxide, butylene oxide, and any mixtures or combinations thereof, n is 1 to 4, and wherein Rxe2x80x3 is O, N, SO2N, methylene, S, N(R5), wherein R5 is alkyl; wherein if Rxe2x80x3 is O or SO2N then w=0 or 1, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2, and if Rxe2x80x3 is other than O or SO2N, then w=0-2, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2; and wherein Rxe2x80x2xe2x80x3 is halogen, hydrogen, alkyl, alkoxy, or B.
The present invention also preferably encompasses poly(oxyalkylenated) acetoacetanilide azo colorants of the structure of Formula (IV) 
wherein R is phenyl, polyphenyl, substituted polyphenyl, or substituted phenyl; Rxe2x80x2 is alkyl, phenyl, substituted phenyl, or polyphenyl; A is C1 to C20 alkyl, alkox ether, (EO)k(PO)l(EO)m , or (PO)p(EO)q(PO)r , wherein k=0-30, 1=0-30, m=0-30, wherein k+l+m greater than 1, and wherein p=0-30, q=0-30, and r=0-30, wherein p+q+r greater than 1; wherein B is Rxe2x80x3(gly)w[(EO)x(PO)y(EO)zEG]nxe2x80x3 wherein EG is H or a moiety of Structure (III) 
wherein R4 is C1-C40 alkyl or phenyl; all wherein gly is glycidol, EO is ethylene oxide, and PO is selected from the group consisting of propylene oxide, butylene oxide, and any mixtures or combinations thereof, n is 1 to 4, and wherein Rxe2x80x3 is O, N, SO2N, methylene, S, N(R5), wherein R5 is alkyl or H; wherein if Rxe2x80x3 is O, S, or SO2N then w=0 or 1, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2, and if Rxe2x80x3 is other than O, S, or SO2N, then w=0-2, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2; and wherein Rxe2x80x2xe2x80x3 is halogen, hydrogen, alkyl, alkoxy, or B.
Basically, such a colorant comprises a chromophore having two azo acetoacetanilide moieties and at least two poly(oxyalkylene) chains. Such a compound is prepared by diazotizing an aromatic amine compound, which comprises such poly(oxyalkylene) chains, in reaction with a compound conforming with the formula of Structure (V) 
wherein R is alkyl, phenyl, polyphenyl, or substituted phenyl; E is H, halogen, alkyl, alkoxy, or phenyl; a is 0, 1, or 2, wherein if a is 0 then A is phenyl, polyphenyl, substituted polyphenyl, or substituted phenyl, if a is 1, then A is O, SO2N, methylene, S, N(Rxe2x80x2) or a moiety of Structure (II) 
wherein Rxe2x80x2 is alkyl or hydrogen, and if a is 2, then A is O, SO2, methylene, S, N(Rxe2x80x2), wherein Rxe2x80x2 is alkyl of hydrogen.
Preferably, the poly(oxyalkylene) chains of the inventive colorant comprise nucleophilic terminal groups capable of reacting with at least a portion of certain monomers which couple with bisacetacetoanilide or any such derivatives to form the desired polymeric colorant. Such polymeric colorants, which are normally present as liquids, are usually brightly colored greenish yellow, and are brighter than, show improved base stability, and are extremely lightfast, particularly in comparison with many traditional polymeric colorants. Furthermore, this invention encompasses any article or composition comprising such an inventive colorant or colorants, including, without limitation, waxes, thermoplastics (such as, without limitation, polyolefins, including, again, without limitation, polypropylene, and polyesters, such as polyethylene terephthalate, all without limitation), and thermosets (such as, without limitation, polyurethanes, including, again, without limitation, polyurethane foams).
Preferably, the particular oxyalkylene groups are selected from ethyleneoxy (EO), propyleneoxy (PO), and butyleneoxy (BO) groups. Preferably, are mixtures of EO and PO groups, although the presence of all EO or PO or BO groups may be utilized as well. Preferably, from about 2 to about 300 moles of alkyleneoxy groups are present on each separate polyoxyalkylene pendant group; more preferably from about 2 to 100 moles; and most preferably from about 2 to 15 moles. The term xe2x80x9cpolyoxyalkylenexe2x80x9d is intended to encompass any pendant group which includes at least two alkyleneoxy moieties.
The addition of polyoxyalkylene groups to the bisacetoacetanilide base compound may be accomplished through the reaction of the aforementioned poly(oxyalkylenated) aromatic amine with a number of different compounds possessing the required bis-acetoacetanilide azo groups. The aromatic amine may be of any structure, depending on the desired characteristics available through the presence of different pendant groups on the aromatic amine itself. The potential preferred aromatic amines useful in this respect are those represented by the following Structure (VI) 
wherein Rxe2x80x2xe2x80x3 is H, alkyl, alkoxy, or B; wherein B is Rxe2x80x3(gly)w[(EO)z(PO)Y(EO)xH]nxe2x80x3; wherein gly is glycidol, EO is ethylene oxide, and PO is selected from the group consisting of propylene oxide, butylene oxide, and any mixtures or combinations thereof, n 1 to 4, and wherein Rxe2x80x3 is O, N, SO2, methylene, S, N(R5), wherein R5 is alkyl or R6xe2x80x94Oxe2x80x94R7, wherein R6 and R7 are the same or different and are each individually C1-C4 alkyl; wherein if Rxe2x80x3 is O or SO2 then w=0 or 1, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2, an SO2, then w=0-2, x=0-30, y=0-30, and z=0-30, wherein w+x+y+z greater than 2.
The potential bis-acetoacetanilide azo compounds are thus represented by the above-described described Structures (I) and (IV).
The presence of surfactants, solvents, and the like, may be utilized to alter the solubility, coloring characteristics, and the like, of the ultimate poly(oxyalkylenated) bis-acetoacetanilide azo compounds which would be understood and appreciated by the ordinarily skilled artisan within this particular art.
Preferably, the colorant compound (I) is liquid in nature at ambient temperature and pressure and at substantial purity; however, pasty or waxy colorants are also encompassed within this invention. In order to effectuate coloring of substrates and media, any other standard colorant additives, such as resins, preservatives, surfactants, solvents, antistatic compounds, and the like, may also be utilized within the inventive colorant compound compositions or methods.